|Publication number||US3957625 A|
|Application number||US 05/547,892|
|Publication date||May 18, 1976|
|Filing date||Feb 7, 1975|
|Priority date||Feb 7, 1975|
|Publication number||05547892, 547892, US 3957625 A, US 3957625A, US-A-3957625, US3957625 A, US3957625A|
|Inventors||Bernard A. Orkin|
|Original Assignee||Mobil Oil Corporation|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Referenced by (76), Classifications (8)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The catalytic hydrodesulfurization and hydrofining of hydrocarbon fractions is well known at this stage of the refining art. A great variety of catalysts and processing inovations have also been proposed for use. The primary requisites of the prior art catalysts are that they exhibit a high degree of activity for the hydrogenation reaction to be accomplished so that decomposition of the sulfur compounds in the charge as well as decomposition of nitrogen and/or oxygen compounds will be accomplished. It is also desirable in many of these hydrogenation reactions to minimize the scisson of carbon to carbon bonds resulting in the production of undesired light gases. It is also desirable in some hydrogenation processes to summarize the hydrogenation of some desired constituents comprising the feed being processed. It is known that most of the transitional metal oxides and sulfides which are not poisoned by sulfur, possess desired hydrodesulfurization activity. Some of the best known catalysts suitable for this purpose are cobalt molybdate supported on alumina, nickel-tungsten sulfide on various supports such as alumina and silica-alumina, molybdenum on alumina as well as some vanadium-alumina catalysts alone or promoted with magnesia.
Hydrogenation processes are subject to effecting olefin saturation which not only consumes hydrogen but lowers the octane number of resulting product such as gasoline product. At the present time it is desirable to reduce process economies and in the case of gasoline production it is desirable to maintain process derived gasoline product octane values in conjunction with providing an acceptable sulfur level in the product. This has become increasingly important with the environmental demands for high octane unleaded gasolines satisfying the requirements of the day and near future.
The present invention is concerned with an improved method for producing desired gasoline product quality satisfying a predetermined sulfur restriction.
In a particular aspect the present invention is concerned with the hydrodesulfurization of cracked gasoline under processing restraints and conditions particularly restricting the hydrogenation of olefins and minimizing the loss in (R+O) research octane number. The hydrodesulfurization operation of the present invention is completed in the presence of particularly selective catalyst compositions providing activity for the removal of undesired sulfur to a desired low value without adversely effecting the olefin content of the charge. The particularly selective catalysts found useful in the process of this invention include cobalt-molybdena on alumina and nickel-tungsten sulfide on a support such as alumina and either one promoted with an element selected from the group consisting of barium, magnesium or a rare earth metal.
The processing combination of the present invention is particularly enhanced by hydrofinishing only a selected heavy end portion of the sulfur containing gasoline charge, which heavy end portion will contain a major portion of the undesired sulfur and little of the desired olefins. The desulfurization operation of the present invention is carried out with minimal saturation of desired olefins thereby considerably restricting the lowering of product octane number. The cut point made in the gasoline product for desulfurizing according to this invention will vary considerably within the range of about 180°F. to about 300°F. The cut point will be determined as a function of the permissible product sulfur content and the charge stock sulfur content as well as the amount of desulfurization required.
The desulfurizing operation of the present invention is accomplished at a temperature within the range of 500°F. to 800°F. at a pressure in the range of 50 to 750 psig. The hydrogen to hydrocarbon ratio is preferably within the range of 1 to 10 and a reactant feed space velocity within the range of 2 to 20 LHSV. The catalyst is preferably retained as a fixed bed of catalyst. Fluid catalyst bed systems are also contemplated.
All of the desulfurization runs reported in Tables below were performed in a small isothermal, down-flow reactor. The start-up and run conditions were maintained substantially identical. After an exploratory search for selective catalyst compositions with a charge comprising heptene-1 and thiophene, the data reported below were obtained with the cracked gasoline feed identified in each table.
In Table 1 below, a gasoline product of fluid cracking boiling in the range of 107 to 446°F. and comprising sulfur of about 0.387 wt.%; a Br. No. of 60 and an octane number (R+O) of 91.3 was processed over the catalysts and conditions identified in Table 1.
TABLE 1__________________________________________________________________________DESULFURIZATION OF FCC GASOLINE1 Pressure Temp.Catalyst PSIG °F. LHSV (R+O) % DS2 % SAT3__________________________________________________________________________CoMo/Al 100 600 6 -10.1 93 69 100 600 3 -12.1 96 85 500 600 6 -14.3 91 97 500 600 3 -15.7 96 98CoMo/Alumina 100 600 6 - 8.0 87 36+ RE 100 600 3 -10.2 94 52 500 600 3 -12.1 99 95CoMo/Alumina 100 600 6 - 5.2 92 39+ Ba 100 600 3 - 8.8 94 59 500 600 6 -13.8 90 95CoMo/Alumina 100 600 6 - 2.0 52 13+ Mg 100 600 3 - 3.4 73 21 500 600 3 -13.4 89 97CoMo/Alumina 100 600 6 - 3.9 68 30+ Fe 100 600 3 - 6.3 80 40__________________________________________________________________________ 1 S = .387 Br No. = 60 R+O = 91.3 2 Wt. % desulfurization. 3 As determined by decrease in bromine number.
It is clearly evident from an evaluation of the data of Table 1 that desulfurization of the full boiling range product gasoline was accompanied by a substantial loss in octane number. It is also clear that the cobalt-molybdena-alumina catalyst promoted with barium is superior to all the other catalysts in one or more areas of octane loss, percent desulfurization and percent saturation particularly at the lower pressure condition of 100 psig.
The work reported in Table 1 above was followed by treating with hydrogen for sulfur removal only a high boiling portion of the FCC gasoline and comprising about the bottom 43 percent of the gasoline product of fluid cracking. The untreated portion is combined with the treated portion to form the reconstituted gasoline for improvement determination. The high boiling gasoline charged to the desulfurization operation was a 280°F.+ gasoline boiling product fraction of fluid cracking comprising a sulfur content of 0.235 wt.% and a Br. No. of 15.50. The total FCC gasoline has a sulfur content of 0.123%, a Br. No. of 49.6 and an octane number (R+O) of 92.3. The reconstituted gasoline had a much lower sulfur level without product octane loss as shown by Table 2.
Table 2__________________________________________________________________________DESULFURIZATION OF 280°F. + GASOLINE AND PROPERTIESOF RE-CONSTITUTED GASOLINE Pressure Temp.Catalyst PSIG °F. LHSV Δ (R+O) % DS Br.No.__________________________________________________________________________CoMo/Alumina 100 600 6 -1.3 76 54.1 200 600 6 -1.9 74 54.4 500 600 6 -1.6 76 52.1CoMo/Alumina 100 600 6 +0.1 75 55.8+Ba 200 600 6 +0.1 76 55.3 500 600 6 -0.5 76 54.0 100 600 10 +1.2 69 55.6__________________________________________________________________________
The data of Table 2 show that 75% desulfurization can be achieved when hydrofinishing only a high boiling portion of the gasoline with little loss in (R+O) octane number when using a cobalt-molybdena-alumina catalyst and with substantially no loss when using the barium promoted catalyst.
In Table 3 below the data obtained are presented when processing a 200°F.+ gasoline product of fluid cracking under the desulfurizing conditions and catalysts shown.
Table 3______________________________________DESULFURIZATION OF 200°F. + GASOLINE ANDRECONSTITUTED GASOLINE PROPERTIES Pressure Temp.Catalyst PSIG °F. LHSV Δ R+O % DS______________________________________CoMo/Alumina 100 600 6 -2.1 88 200 600 6 -3.0 89 500 600 6 -3.9 85CoMo/Al+2% Ba 200 600 6 -3.3 90 500 600 6 -3.6 87CoMo/Al+4% Ba 100 600 6 -1.0 84 200 600 6 -1.2 89 500 600 6 -3.0 86CoMo/Al+10% Ba 100 600 6 +0.2 58 200 600 6 +0.4 59 500 600 6 +0.1 70CoMo/Al+4% Mg 100 600 6 -0.5 86 200 600 6 -1.8 89 500 600 6 -3.0 87CoMo/Al+4% Cd 100 600 6 -0.2 78 200 600 6 -0.7 85 500 600 6 -1.8 83CoMo/Al+4% RE 100 600 6 -1.3 89 200 600 6 -2.7 88 500 600 6 -2.7 85______________________________________ Charge S = .155% Br. No. = 45.0 (R+O) Octane Number = 92.3 Bottoms (67%) S = .219% Br. No. = 25.8
It is clear from the data of Table 3, that the barium promoted catalyst provided better overall results than the cobalt-molybdena catalyst containing no barium. It is also noted that a catalyst containing as much as 10 percent barium realized no significant octane loss under the lower desulfurizing results. The superiority of the barium promoted catalyst is clearly shown by the data presented above.
To facilitate a better understanding of the concepts of the present invention reference is now had to FIG. 1 which is a plot of data showing the sulfur content of gasoline products of cracking at various boiling points. In the specific example of FIG. 1 it is noted that the gasoline products do not exceed a cumulative sulfur level of about 0.025 wt. percent until you reach about a 55 percent boiling point. It is also noted that the cumulative sulfur level rapidly increases after you reach about the 75 percent boiling point.
In FIG. 2, the olefin content of the gasoline product reported in FIG. 1 is provided. The graph of FIG. 2 shows that one of the gasoline products has a much higher olefin content than the other. These curves also indicate that a significant portion of the olefin content of the gasoline product occurs in the front end thereof. For example, in the curve represented by circles, which is the flatter curve, the cumulative olefin content above the 60 percent boiling point is relatively small. Thus when deslfurizing only a selected high boiling portion of the gasoline product such as that boiling above about its 60 percent boiling point, a significant sulfur reduction can be achieved with a limited reduction in olefin content.
Therefore the method and concepts of the present invention contemplate hydrofinishing all or selected portions of a sulfur containing gasoline product to provide a product of desired sulfur content without significant octane loss and the portion selected for hydrofinishing will be chosen as a function of the sulfur content of the gasoline to be processed and the sulfur reduction needed to meet predetermined requirements. As indicated above, the sulfur content of the charge relied upon to produce a cracked gasoline product will also influence the cut point selection referred to above. In any of these processing variations, it is proposed to use a barium modified cobalt-molybdate desulfurization catalyst comprising less than 10 weight percent but above about 2 weight percent barium.
Having thus generally described the invention and presented examples in support thereof, it is to be understood that no undue restrictions are to be imposed by reason thereof except as defined by the following claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2070295 *||Sep 15, 1933||Feb 9, 1937||Universal Oil Prod Co||Treatment of hydrocarbon oils|
|US2114852 *||Aug 11, 1936||Apr 19, 1938||Shell Dev||Process for desulphurizing mineral oil distillates|
|US2911359 *||Apr 30, 1956||Nov 3, 1959||Union Oil Co||Desulfurization process and catalyst|
|US3116233 *||Dec 30, 1960||Dec 31, 1963||Shell Oil Co||Low-temperature selective hydrogenation of dienes|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4062762 *||Sep 14, 1976||Dec 13, 1977||Howard Kent A||Process for desulfurizing and blending naphtha|
|US4314901 *||Jul 15, 1980||Feb 9, 1982||Phillips Petroleum Company||Catalytic hydrodesulfurization of an organic sulfur compound contained in gasoline|
|US5266188 *||Dec 5, 1991||Nov 30, 1993||Amoco Corporation||Selective hydrotreating|
|US5290427 *||Aug 5, 1992||Mar 1, 1994||Mobil Oil Corporation||Gasoline upgrading process|
|US5308471 *||Jul 20, 1992||May 3, 1994||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US5318690 *||Jan 7, 1993||Jun 7, 1994||Mobil Oil Corporation||Gasoline upgrading process|
|US5320742 *||Oct 19, 1992||Jun 14, 1994||Mobil Oil Corporation||Gasoline upgrading process|
|US5326463 *||Oct 28, 1992||Jul 5, 1994||Mobil Oil Corporation||Gasoline upgrading process|
|US5346609 *||Aug 15, 1991||Sep 13, 1994||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US5348641 *||May 8, 1992||Sep 20, 1994||Mobil Oil Corporation||Gasoline upgrading process|
|US5348928 *||May 6, 1993||Sep 20, 1994||Amoco Corporation||Selective hydrotreating catalyst|
|US5352354 *||Jun 1, 1992||Oct 4, 1994||Mobil Oil Corporation||Gasoline upgrading process|
|US5360532 *||Apr 2, 1993||Nov 1, 1994||Mobil Oil Corporation||Gasoline upgrading process|
|US5391288 *||Jun 10, 1993||Feb 21, 1995||Mobil Oil Corporation||Gasoline upgrading process|
|US5397455 *||Aug 11, 1993||Mar 14, 1995||Mobil Oil Corporation||Gasoline upgrading process|
|US5399258 *||Dec 10, 1992||Mar 21, 1995||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US5401389 *||Oct 12, 1993||Mar 28, 1995||Mobil Oil Corporation||Gasoline-cycle oil upgrading process|
|US5407559 *||Jun 1, 1992||Apr 18, 1995||Mobil Oil Corporation||Gasoline upgrading process|
|US5409596 *||Mar 12, 1992||Apr 25, 1995||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US5411658 *||Oct 8, 1993||May 2, 1995||Mobil Oil Corporation||Gasoline upgrading process|
|US5413696 *||Jun 1, 1992||May 9, 1995||Mobile Oil Corporation||Gasoline upgrading process|
|US5413697 *||Jul 14, 1992||May 9, 1995||Mobil Oil Corporation||Gasoline upgrading process|
|US5413698 *||Aug 5, 1992||May 9, 1995||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US5484756 *||May 17, 1993||Jan 16, 1996||Nikki-Universal Co., Ltd.||Hydrodesulfurization catalyst and preparation thereof|
|US5500108 *||Sep 9, 1994||Mar 19, 1996||Mobil Oil Corporation||Gasoline upgrading process|
|US5503734 *||Dec 30, 1994||Apr 2, 1996||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US5510016 *||Sep 9, 1994||Apr 23, 1996||Mobil Oil Corporation||Gasoline upgrading process|
|US5536391 *||Jan 17, 1995||Jul 16, 1996||Howley; Paul A.||Production of clean distillate fuels from heavy cycle oils|
|US5582714 *||Mar 20, 1995||Dec 10, 1996||Uop||Process for the removal of sulfur from petroleum fractions|
|US5599439 *||Oct 14, 1994||Feb 4, 1997||Mobil Oil Corporation||Gasoline and reformate upgrading process|
|US5603824 *||Aug 3, 1994||Feb 18, 1997||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US5643441 *||Apr 24, 1995||Jul 1, 1997||Mobil Oil Corporation||Naphtha upgrading process|
|US5865987 *||May 23, 1997||Feb 2, 1999||Mobil Oil||Benzene conversion in an improved gasoline upgrading process|
|US5865988 *||May 23, 1997||Feb 2, 1999||Mobil Oil Corporation||Hydrocarbon upgrading process|
|US6007704 *||Sep 23, 1997||Dec 28, 1999||Institut Francais Du Petrole||Process for the production of catalytic cracking gasoline with a low sulphur content|
|US6126814 *||Feb 2, 1996||Oct 3, 2000||Exxon Research And Engineering Co||Selective hydrodesulfurization process (HEN-9601)|
|US6315890||Nov 10, 1999||Nov 13, 2001||Exxonmobil Chemical Patents Inc.||Naphtha cracking and hydroprocessing process for low emissions, high octane fuels|
|US6398949 *||Nov 2, 2000||Jun 4, 2002||Phillips Petroleum Company||Sapo-supported hydrodesulfurization catalyst and processes therefor and therewith|
|US6455750||Nov 10, 1999||Sep 24, 2002||Exxonmobil Chemical Patents Inc.||Process for selectively producing light olefins|
|US6540907||Jul 9, 2001||Apr 1, 2003||Uop Llc||Fractionation for full boiling range gasoline desulfurization|
|US6599417 *||Jan 21, 2000||Jul 29, 2003||Bp Corporation North America Inc.||Sulfur removal process|
|US6602403||Nov 10, 1999||Aug 5, 2003||Exxonmobil Chemical Patents Inc.||Process for selectively producing high octane naphtha|
|US6602405 *||Jan 21, 2000||Aug 5, 2003||Bp Corporation North America Inc.||Sulfur removal process|
|US6610197 *||Oct 12, 2001||Aug 26, 2003||Exxonmobil Research And Engineering Company||Low-sulfur fuel and process of making|
|US6623627||Jul 9, 2001||Sep 23, 2003||Uop Llc||Production of low sulfur gasoline|
|US6641716||Apr 18, 2000||Nov 4, 2003||Exxonmobil Research And Engineering Company||Method for isolating enriched source of conducting polymers precursors using monohydroxyl alcohol treating agent|
|US6642421||Apr 18, 2000||Nov 4, 2003||Exxonmobil Research And Engineering Company||Method for isolating enriched source of conducting polymers precursors|
|US6726835||Dec 17, 2002||Apr 27, 2004||Uop Llc||Fractionation for full boiling range gasoline desulfurization|
|US6803494||May 19, 2000||Oct 12, 2004||Exxonmobil Chemical Patents Inc.||Process for selectively producing propylene in a fluid catalytic cracking process|
|US6838060||Nov 5, 1999||Jan 4, 2005||Institut Francais Dupetrole||Process and apparatus for the production of catalytic cracking gasoline with a low sulphur content|
|US7005058||May 8, 2002||Feb 28, 2006||Uop Llc||Process and apparatus for removing sulfur from hydrocarbons|
|US7153415 *||Nov 1, 2002||Dec 26, 2006||Catalytic Distillation Technologies||Process for the treatment of light naphtha hydrocarbon streams|
|US7341657||Dec 22, 2003||Mar 11, 2008||China Petroleum & Chemical Corporation||Process for reducing sulfur and olefin contents in gasoline|
|US7361265||Mar 12, 2003||Apr 22, 2008||Petroleo Brasileiro S.A.-Petrobras||Process for the selective hydrodesulfurization of olefinic naphtha streams|
|US7754068||Nov 21, 2006||Jul 13, 2010||Petroleo Brasileiro S.A.-Petrobras||Process for the selective hydrodesulfurization of naphtha streams|
|US7785461||Apr 6, 2005||Aug 31, 2010||Petroleo Brasileiro S.A. - Petrobras||Process for selective hydrodesulfurization of naphtha|
|US7837861||Sep 14, 2007||Nov 23, 2010||Exxonmobil Research & Engineering Co.||Process for benzene reduction and sulfur removal from FCC naphthas|
|US20020169350 *||Jul 3, 2002||Nov 14, 2002||Steffens Todd R.||Process for selectively producing light olefins|
|US20040000506 *||Nov 1, 2002||Jan 1, 2004||Catalytic Distillation Technologies||Process for the treatment of light naphtha hydrocarbon streams|
|US20040222130 *||Jun 10, 2004||Nov 11, 2004||Stuntz Gordon F.||Low-sulfur fuel|
|US20050133410 *||Dec 22, 2003||Jun 23, 2005||China Petroleum & Chemical Corporation||Process for reducing sulfur and olefin contents in gasoline|
|US20060096893 *||Apr 6, 2005||May 11, 2006||Petroleo Brasileiro S.A. - Petrobras||Process for selective hydrodesulfurization of naphtha|
|US20070267326 *||Nov 21, 2006||Nov 22, 2007||Petroleo Brasileiro S.A. - Petrobras||Process for the selective hydrodesulfurization of naphtha streams|
|US20080116112 *||Sep 14, 2007||May 22, 2008||Exxonmobil Research And Engineering Company||Process for benzene reduction and sulfur removal from FCC naphthas|
|CN1694945B||Sep 16, 2003||May 26, 2010||催化蒸馏技术公司||Process for the treatment of light naphtha hydrocarbon streams|
|CN101275085B||Mar 30, 2007||Jan 25, 2012||中国石油化工股份有限公司||Combined method for gasoline desulfurization|
|EP0267833A1 *||Oct 21, 1987||May 18, 1988||Societe Nationale Elf Aquitaine (Production)||Process for the desulfurization of ternic oils|
|EP0582403A1 *||Jul 21, 1993||Feb 9, 1994||Texaco Development Corporation||Hydrotreating of cracked naptha|
|EP1349905A1 *||Oct 30, 2001||Oct 8, 2003||ExxonMobil Research and Engineering Company||Low-sulfur fuel|
|EP1349905A4 *||Oct 30, 2001||Feb 2, 2005||Exxonmobil Res & Eng Co||Low-sulfur fuel|
|WO1995010579A1 *||Sep 21, 1994||Apr 20, 1995||Mobil Oil Corporation||Gasoline/cycle oil upgrading process|
|WO1995010580A1 *||Sep 16, 1994||Apr 20, 1995||Mobil Oil Corporation||Gasoline upgrading process|
|WO1996007714A1 *||Aug 15, 1995||Mar 14, 1996||Mobil Oil Corporation||Gasoline upgrading process|
|WO1996030463A1 *||Feb 14, 1996||Oct 3, 1996||Mobil Oil Corporation||Naphtha upgrading process|
|WO2002036718A1 *||Oct 30, 2001||May 10, 2002||Exxonmobil Research And Engineering Company||Low-sulfur fuel|
|WO2004041971A1 *||Sep 16, 2003||May 21, 2004||Catalytic Distillation Technologies||Process for the treatment of light naphtha hydrocarbon streams|
|U.S. Classification||208/211, 208/218, 208/212|
|International Classification||B01J23/887, C10G45/08|
|Cooperative Classification||B01J23/8872, C10G2400/02|